Herbicidal compounds

ABSTRACT

A compound of formula (I): ##STR1## or a salt, enamine or the like, acylate, sulphonate, carbamate or ether derivative thereof; wherein X, X 1  and X 2  are independently oxygen or sulphur, R 1  is an optionally substituted heterocyclic or cycloalkyl group, and Y is an optionally substituted C 2  -C 4  alkylene group which is optionally interposed by an oxygen atom, a group ##STR2## a group ##STR3## or an optionally mono-substituted nitrogen atom, wherein p is 0, 1 or 2, s is 0 or 1 and R b  is alkyl or alkoxy; provided that when X, X 1  and X 2  are oxygen, R 1  is not pyridyl or pyrimidinyl. Processes for the preparation of these compounds and herbicidal compositions containing them are also described and claimed.

This is a division of application Ser. No. 08/102,004, filed Aug. 4,1993, now U.S. Pat. No. 5,426,091, which is a division of applicationSer. No. 07/819,080, filed Jan. 10, 1992, now U.S. Pat. No. 5,250,501,which is a division of application Ser. No. 07/595,710, filed Oct. 9,1990, now U.S. Pat. No. 5,098,464, which is a continuation ofapplication Ser. No. 07/170,389, filed Mar. 18, 1988, now abandoned.

The present invention relates to certain herbicidally active substitutedcyclic diones, to processes for their preparation and to compositionscontaining them.

Herbicidal compounds containing a cyclohexane dione coupled to an arylgroup are described and claimed for example in EP-A-90262, EP-A-137,963,EP-A-135,191 and EP-A-186119.

According to the present invention there is provided a compound offormula (I): ##STR4## or a salt, enamine or the like, acylate,sulphonate, carbamate or ether derivative thereof; wherein X, X¹ and X²are independently oxygen or sulphur; R¹ is an optionally substitutedheterocyclic or cycloalkyl group; and Y is optionally substituted C₂ -C₄alkylene group which is optionally interposed by an oxygen atom, a group##STR5## a group ##STR6## or an optionally mono-substituted nitrogenatom, wherein p is 0, 1 or 2, s is 0 or 1 and R^(b) is alkyl or alkoxy;provided that when X, X¹ and X² are oxygen, R¹ is not pyridyl orpyrimidinyl.

Compounds of formula (I) can exist in a number of tautomeric forms, forexample: ##STR7## wherein R¹, X, X¹, X² and Y are as defined in relationto formula (I). Further tautomers exist when Y contains a hydrogensubstituent on a carbon atom adjacent to the carbon bearing X¹ or X². Itis intended that all such forms are included within the scope of theinvention.

When the compound contains a free hydroxy or thiol group in this way, itmay be derivatised to form salts, in particular agriculturallyacceptable salts, enamines or the like, acylates, sulphonates,carbamates or ethers.

Suitable agriculturally acceptable salts include salts such as sodium,potassium, calcium and ammonium salts.

Examples of ammonium salts include salts with ions of formula N⁺ R^(c)R^(d) R^(e) R^(f) where R^(c), R^(d), R^(e) and R^(f) are independentlyselected from hydrogen and C₁₋₁₀ alkyl optionally substituted by, forexample, hydroxy. Suitably when any of R^(c), R^(d), R^(e) or R^(f) areoptionally substituted alkyl, they contain from 1 to 4 carbon atoms.

Suitable acylate or ether derivatives are compounds wherein the OHmoiety has been converted to a group of formula --OCOR² or --OR²respectively wherein R² is optionally substituted alkyl having forexample from 1 to 6 carbon atoms, or aryl such as phenyl.

Suitable carbamate derivatives are compounds wherein the OH moiety hasbeen converted to a group ##STR8## wherein R³ and R⁴ are independentlyhydrogen or a group R² as defined above.

Preferably X, X¹ and X² are oxygen.

As used herein the term "enamine or the like" refers to derivativeswhere one of X or X¹ is oxygen and the other is replaced by NR³ R⁴, halosuch as fluoro or SR².

These derivatives can be prepared by conventional methods.

Suitable heterocyclic groups R¹ include mono- or fused bicyclo-heterocyclic rings which may be aromatic or non-aromatic. Suitably R¹includes up to ten ring atoms up to five preferably three of which maybe selected from oxygen, nitrogen and sulphur.

When R¹ is a monocyclic ring, it is suitably a heteroaryl group havingup to 7 ring atoms up to 3 of which are selected from oxygen, nitrogenand sulphur. As used here in the term "heteroaryl" means aromaticheterocyclic.

When R¹ is a fused bicyclic ring, one or both of the rings may containheteroatoms and it may be bonded to the group ##STR9## by way of eitherof these rings.

Examples of such heterocyclic groups including furyl, thienyl, pyrrolyl,pyrazolyl, pyridyl, pyrimidinyl, imidazoyl, triazolyl, dithiol,oxathiol, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, oxadiazolyl,thiodiazolyl, oxatriazolyl, dioxazolyl, oxathiazolyl, oxathiol,dioxinyl, pyridazinyl, pyrazinyl, piperazinyl, priazinyl, oxazinyl,isoxazinyl, oxathiazinyl, morphlinyl, azepinyl, oxepinyl, thiepinyl,diazepinyl, benzofuranyl, isobenzofuranyl, benzothienyl,isobenzothienyl, thionaphthalenyl, isothionaphthalenyl, indolyl,isoindolyl, indazolyl, indoleninyl, isobenzazolyl, pyranopyrrolyl,isoindazolyl, indoxazinyl, benzoxazolyl, benzopyranyl, quinolinyl,isoquinolinyl, cinnolinyl, phthalazinyl, quinoxalinyl, quinazolinyl,naphthyridinyl, pyridopyridinyl, pyranyl, thiopyranyl, chromenyl,thiachromenyl, benzoxazinyl, benzisoxazinyl and purine.

Particular examples of heterocyclic groups R¹ include furyl, thiazolyl,thienyl, benzoxazolyl, pyrazolyl, pyridazinyl, pyrazinyl, benzoxazolyl.

These heterocycles may be linked either through carbon atom or whenpossible through a nitrogen atom.

Suitable cycloalkyl groups R¹ contain up to 10 ring carbon atoms,preferably up to 7 ring atoms.

Suitable optional substituents for the groups R¹ and R⁸ include one ormore groups selected from oxo, mercapto, halo, such as fluoro, chloro,bromo or iodo, nitro, cyano, amino, mono or dialkylamino, amido, alkyl,alkenyl, alkynyl, cycloalkyl, haloalkyl such as trifluoromethyl,haloalkoxy such as trifluoromethoxy, optionally substituted aryl such asphenyl or naphthyl, hydroxy, alkoxy, alkoxycarbonyl, alkylcarbonyl,mono- or dialkylcarbamoyl, alkylthio, alkylsulphinyl, alkylsulphonyl,sulphonamido, alkylcarbonyloxy, alkylcarbonylamino or heterocyclyl suchas pyridyl and thienyl.

The substituents may be attached to a carbon and/or nitrogen atom of thegroup R¹.

In the above-mentioned list of substituents, the alkyl, alkenyl oralkynyl groups or moieties preferably contain from 1 to 6 carbon atoms.Suitable optional substituents for the aryl groups include halo such asfluoro, chloro or bromo, C₁₋₆ alkyl or C₁₋₆ alkoxy.

In a preferred embodiment, is a 6-membered heteroaryl ring for examplefrom one or two nitrogen atoms such as pyridyl, pyrimidinyl, pyridazinylor pyrazinyl.

In another preferred embodiment, R¹ is a five membered heteroaryl groupor comprises a five-membered heteroaryl group.

For example, R¹ is selected from groups of formula: ##STR10## wherein R⁵is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl or optionallysubstituted aryl such as phenyl; R⁶, R⁷ and R⁸ independently are (1)hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁-C₄ alkyl, preferably methyl; (4) haloalkoxy, preferably OCF₃ ; (5) C₁-C₄ alkoxy, preferably methoxy; (6) cyano; (7) nitro; (8) C₁ -C₄haloalkyl, preferably trifluoromethyl; (9) R⁹ SOn-- wherein n is theinteger 0, 1, or 2, preferably 2; and R⁹ is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen, cyano, C₁ -C₂ alkoxy or C₁-C₂ alkylthio, preferably chloromethyl, difluoromethyl, trifluoromethylor cyanomethyl;

(c) phenyl; or

(d) benzyl; (10) --NR¹⁰ R¹¹ wherein R¹⁰ and R¹¹ independently arehydrogen or C₁ -C₄ alkyl; (11) R¹² C(O)-- wherein R¹² is C₁ -C₄ alkyl orC₁ -C₄ alkoxy; (12) --SO₂ NR¹⁰ R¹¹ wherein R¹⁰ and R¹¹ are as definedabove; or (13) --N(R¹⁰)C(O)R¹¹ wherein R¹⁰ and R¹¹ are as defined above.

In particular R¹ is a group of formula: ##STR11## wherein R⁵ and R⁶ areas defined above.

In particular R⁵ is C₁₋₆ alkyl which may be straight or branched oroptionally substituted phenyl, such as phenyl, p-chlorophenyl,p-methoxyphenyl or p-methylphenyl.

Preferred groups R⁶ are haloalkyl in particular trifluoromethyl.

In a further preferred embodiment R¹ is a bicyclic group of formula##STR12## wherein R⁶, R⁷ and R⁸ are as defined above;

One of R¹² or R¹³ is --N═ and the other is C(R¹⁴) wherein R¹⁴ ishydrogen, halogen, such as chlorine, fluorine or bromine; C₁ -C₄ alkyl,such as methyl; OCF₃ ; C₁ -C₄ alkoxy, such as methoxy; cyano; nitro; C₁-C₄ haloalkyl, such as trifluoromethyl; R¹⁵ SOm wherein m is the integer0, 1 or 2, preferably 2; and R¹⁵ is C₁ -C₄ alkyl, such as methyl.

In addition R¹ may be a bicyclic group of sub formula ##STR13## whereinZ is a five or six membered saturated or unsaturated fused ringcontaining up to three heteroatoms selected from oxygen, sulphur andnitrogen. Preferably the ring Z contains two oxygen atoms or an oxygenor sulphur and a nitrogen atom. Thus examples of the group R¹ include##STR14## where R⁶ is as defined above. Suitable optional substituentsfor the group Y include those listed above for R¹. In additionsubstituents on adjacent carbon atoms in the group Y may be joinedtogether to form a fused ring system. The fused ring may be aromatic ornon-aromatic and may be optionally substituted by one or moresubstituents listed above for R¹. For example, the group ##STR15## maybe the group: ##STR16## Preferably Y is a group of formula: ##STR17##wherein R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ and are independently selectedfrom hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkanoyl or --CO₂ R²² wherein R²² isC₁₋₄ alkyl or R¹⁶ and R¹⁷ or R¹⁸ and R¹⁹ or R²⁰ and R²¹ together withthe carbon atom to which they are attached form a C₃₋₆ cycloalkyl ring;and q is 0 or 1. Most preferably q is 1.

Other examples of the group Y are ##STR18## wherein R¹⁶, R¹⁷, R¹⁸, R¹⁹,R²⁰, R^(b), s and p are as hereinbefore defined and R²³ is alkyl oralkoxy preferably having up to 6 carbon atoms.

In particular the group ##STR19## is a group of formula ##STR20##

A suitable alkanoyl group for R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ is acetyl.

Preferably only one of R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ is eitheralkanoyl or --CO₂ R².

Preferably R¹⁶, R¹⁷, R¹⁸ l , R¹⁹, R²⁰ and R²¹ are hydrogen or C₁₋₄ alkylin particular C₁₋₂ alkyl.

Most preferably R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ R²¹ hydrogen or methyl.

A particularly preferred sub-group of compounds are compound of formula(IA): ##STR21## or a salt, acylate or sulphonate derivative thereof;wherein R²⁵ is an optionally substituted heteroaryl group, R¹⁶, R¹⁷, R²⁰and R²¹ are as hereinbefore defined, provided that at least R¹⁶ and R¹⁷or R²⁰ and R²¹ are not both hydrogen and that not more than two of R¹⁶,R¹⁷, R²⁰ and R²¹ are C₁₋₄ alkanoyl or --CO₂ R²².

Most preferably R¹⁶, R¹⁷, R²⁰ and R²¹ are C₁₋₄ alkyl in particularmethyl.

Examples of compounds of formula (I) are set out in Tables I and II.

                                      TABLE I                                     __________________________________________________________________________     ##STR22##                                                                    Compound                                    CHARACTERISING                    NO.     R.sup.1          R.sup.16                                                                         R.sup.17                                                                         R.sup.18                                                                         R.sup.19                                                                          R.sup.20                                                                         R.sup.21                                                                         DATA                              __________________________________________________________________________             ##STR23##       H  H  CH.sub.3                                                                         CH.sub.3                                                                          H  H  M.sup.+ 250 δ 8.14(d,                                                   1); 7.70 (d, 1); 7.12(dd, 1);                                                 2.54 (broad s, 4); 1.12(s,                                                    6); 1760(broad s, 1).             2                                                                                      ##STR24##       H  H  H  H   H  H  M.sup.+  222 δ 8.06(d,                                                  1); 7.68 (d, 1); 7.10(dd, 1);                                                 2.64 (broad s, 4); 2.04(M,                                                    2); 1730(broad s, 1).             3                                                                                      ##STR25##       H  H  CH.sub.3                                                                         CH.sub.3                                                                          H  H  MH.sup.+ 319, (MCl).sup.+                                                     283 δ 6.80(s, 1);                                                       2.64(s, 2); 2.40(s, 2);                                                       1.12(s, 6); 16.75(s, 1) all                                                   peaks broad.                      4                                                                                      ##STR26##       H  H  H  H   H  H  MH.sup.+  291, (MCl).sup.+                                                    255 δ 6.80(s, 1);                                                       2.74(t, 2); 2.50(t, s);                                                       2.04(M, 2); 16.94(s, 1).          5                                                                                      ##STR27##       H  H  CH.sub.3                                                                         CH.sub.3                                                                          H  H  M.sup.+  330 δ 8.0(d,                                                   1); 7.12 (d, 1); 2.54(broad                                                   s, 4); 1.12(s, 6).                6                                                                                      ##STR28##       H  H  H  H   H  H  M.sup.+  236, M.sup.+                                                         --CH.sub.3 221 δ 7.46                                                   (d, 1); 6.87(d,                                                               1); 2.61(broad, 4), 2.06(M,                                                   2); 16.6(broad s, 1).             7                                                                                      ##STR29##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  H-NMR(CDCl.sub.3); δ                                                    1.31 (s, 2 CH.sub.3), 1.91(s,                                                 CH.sub.3), 2.71(t, CH.sub.2),                                                 7.62(s 2 ar.H); MS: 168, 170,                                                 196, 198, 224, 226, 280,                                                      (M.sup.+), 282                    8                                                                                      ##STR30##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  H-NMR(CDCl.sub.3); δ                                                    1.06(s, CH.sub.3), 1.23(s,                                                    CH.sub.3), 1.85(t, CH.sub.2),                                                 .61(t, CH.sub.2), 8.45(s,                                                     ar.H), 8.50(s, ar.H); MS:                                                     113, 128, 130, 141, 143, 168,                                                 170, 196, 198, 209, 211, 224,                                                 226, 265, 267, 280(M.sup.+),                                                  282                               9                                                                                      ##STR31##       H  H  H  H   H  H                                                                                 ##STR32##                        10                                                                                     ##STR33##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR34##                        11                                                                                     ##STR35##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR36##                        12                                                                                     ##STR37##       H  H  H  H   H  H                                                                                 ##STR38##                        13                                                                                     ##STR39##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR40##                        14                                                                                     ##STR41##       H  H  H  H   H  H                                                                                 ##STR42##                        15                                                                                     ##STR43##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR44##                        16                                                                                     ##STR45##       H  H  H  H   H  H                                                                                 ##STR46##                        17                                                                                     ##STR47##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR48##                        18                                                                                     ##STR49##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR50##                        19                                                                                     ##STR51##       H  H  H  H   H  H                                                                                 ##STR52##                        20                                                                                     ##STR53##       H  H  H  H   H  H                                                                                 ##STR54##                        21                                                                                     ##STR55##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR56##                        22                                                                                     ##STR57##       H  H  H  H   H  H                                                                                 ##STR58##                        23                                                                                     ##STR59##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR60##                        24                                                                                     ##STR61##       H  H  H  H   H  H                                                                                 ##STR62##                        25                                                                                     ##STR63##       H  H  CH.sub.3                                                                         CH.sub.3                                                                          H  H  H-NMR(CDCl.sub.3): δ                                                    1.14(s, 2CH.sub.3), 2.42(s,                                                   2CH.sub.2), 3.90 (s,CH.sub.3                                                  N), 6.15(dd, ar.H), 6.86 (m,                                                  2 ar.H); MS: 108, 135, 167,                                                   1230, 247(M.sup.+)                26                                                                                     ##STR64##       H  H  H  H   H  H  H-NMR(CDCl.sub.3): δ                                                    2.10(m, CH.sub.2), 2.58(br.m                                                  2CH.sub.2), 3.88 (s, CH.sub.3                                                 N), 7.04(s, ar.H), 7.3-                                                       7.7(m, 4 ar.H); MS: 130, 131,                                                 39, 144, 158, 269(M.sup.+)        27                                                                                     ##STR65##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  H-NMR(CDCl.sub.3): δ                                                    1.30(s, 2CH.sub.3), 1.90(t,                                                   CH.sub.2), 2.62(t, CH.sub.2),                                                 .84(s, CH.sub.3 N), 6.88(s,                                                   ar.H), 7.00-7.6(m, 4 ar.H);                                                   MS: 130, 131, 158, 167, 185,                                                  213, 241, 280, 297(M.sup.+)       28                                                                                     ##STR66##       H  H  CH.sub.3                                                                         CH.sub.3                                                                          H  H  H-NMR(CDCl.sub.3): δ                                                    1.10(s, 2CH.sub.3L ), 2.38(s,                                                 2CH.sub.2), 3.90(s, CH.sub.3                                                  N), 6.90(s, ar.H), 7.00-7.55                                                  (m, 4 ar.H); MS: 130, 131,                                                    158, 167, 280, 297(M.sup.+)       29                                                                                     ##STR67##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  H-NMR(CDCl.sub.3): δ                                                    1.23(s, 2CH.sub.3L ), 1.91(t,                                                 CH.sub.2), 2.70(t, CH.sub.2),                                                 .16(s, CH.sub.3 SO.sub.2),                                                    4.03(s, CH.sub.3 N), 6.54(d,                                                  ar.H), 6.85(d, ar.H); MS:                                                     159, 167, 172, 173, 186, 246,                                                 325(M.sup.+)                      30                                                                                     ##STR68##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR69##                        31                                                                                     ##STR70##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR71##                        32                                                                                     ##STR72##       H  H  CH.sub.3                                                                         CH.sub.3                                                                          H  H                                                                                 ##STR73##                        33                                                                                     ##STR74##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR75##                        34                                                                                     ##STR76##       H  H  H  H   H  H  MS: 128, 129, 143, 156, 173,                                                  211, 267(M.sup.+)                 35                                                                                     ##STR77##       H  H  H  H   H  H  mp. 110-130° C.            36                                                                                     ##STR78##       H  H  H  H   H  H                                                                                 ##STR79##                        37                                                                                     ##STR80##       H  H  H  H   H  H                                                                                 ##STR81##                        38                                                                                     ##STR82##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  H-NMR(CDCl.sub.3): δ                                                    1.32(s, 2CH.sub.3), 1.98(t,                                                   CH.sub.2), 2.80(t, CH.sub.2);                                                 S: 180, 182, 184, 227, 229,                                                   255, 257, 284(M.sup.+ --Cl),                                                  286                               39                                                                                     ##STR83##       H  H  H  H   H  H                                                                                 ##STR84##                        40                                                                                     ##STR85##       H  H  H  H   H  H                                                                                 ##STR86##                        41                                                                                     ##STR87##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                                                                 ##STR88##                        42                                                                                     ##STR89##       H  H  H  H   H  H                                                                                 ##STR90##                        43                                                                                     ##STR91##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  H-NMR(CDCl.sub.3): δ                                                    1.13(br.s. 2CH.sub.3),                                                        1.78(t, CH.sub.2), 2.6                                                        (br.m.CH.sub.2)(3.88(s,                                                       CH.sub.3 N), 7.85(s, ar.H);                                                   MS: 177, 232, 247, 260,                                                       316(M.sup.+)                      44                                                                                     ##STR92##       H  H  H  H   H  H  mp. 60-64° C.              45                                                                                     ##STR93##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  glass                             46                                                                                     ##STR94##       H  H  H  H   H  H  Semi solid                        47                                                                                     ##STR95##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  Semi solid                        48                                                                                     ##STR96##       H  H  H  H   H  H  Dark oil                          49                                                                                     ##STR97##       H  H  H  H   H  H  Oil                               50                                                                                     ##STR98##       CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  Oil                               51                                                                                     ##STR99##       H  H  H  H   H  H  mp 128-131° C.             52                                                                                     ##STR100##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  Glass                             53                                                                                     ##STR101##      H  H  H  H   H  H  Mpt. 90-100° C.            54                                                                                     ##STR102##      H  H  H  H   H  H  Mpt 110-114° C.            55                                                                                     ##STR103##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  Mpt 105-108° C.            56                                                                                     ##STR104##      H  H  H  H   H  H  Mpt. 112-115° C.           57                                                                                     ##STR105##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  Mpt 71-76° C.              58                                                                                     ##STR106##      H  H  H  H   H  H  mp. 31-35° C.              59                                                                                     ##STR107##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H                                    60                                                                                     ##STR108##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  mp. 75-82° C.              61                                                                                     ##STR109##      H  H  H  H   H  h  mp. 70-74                         62                                                                                     ##STR110##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  oil                               63                                                                                     ##STR111##      H  H  H  H   H  H  mp. 126-128° C.            64                                                                                     ##STR112##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  mp. 98-100° C.             65                                                                                     ##STR113##      H  H  H  H   H  H  mp. 100-102° C.            66                                                                                     ##STR114##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  oil                               67                                                                                     ##STR115##      H  H  H  H   H  H  mp. 135-145                       68                                                                                     ##STR116##      H  H  H  H   H  H  mp. 104-106° C.            69                                                                                     ##STR117##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  mp. 60-65° C.              70                                                                                     ##STR118##      H  H  H  H   H  H  mp. 94-104° C.             71                                                                                     ##STR119##      CH.sub.3                                                                         CH.sub.3                                                                         H  H   H  H  mp. 89-93° C.              72                                                                                     ##STR120##      H  H  H  H   H  H  .sup.1 H NMR(CDCl.sub.3):                                                     δ 2.06(t, CH.sub.2);                                                    2.42(t CH.sub.2); 2.70(t,                                                     CH.sub.2); 4.23(m,                                                            2CH.sub.2); 6.94(m, ar, H);                                                   7.06(tr, s.OH)                    73                                                                                     ##STR121##      H  H  H  H   H  H  mp. 80-82° C.              74                                                                                     ##STR122##      H  H  H  H   H  H  mp. 156-7° C.              75                                                                                     ##STR123##      H  H  H  H   H  H  mpt. 139-140° C.           76                                                                                     ##STR124##      H  H  H  H   H  H  mpt. 143-144° C.           77                                                                                     ##STR125##      H  H  H  H   H  H  mpt. 105-106° C.           __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________     ##STR126##                                                                   COMPOUND                         CHARACTERISING                               NO.     R.sup.1      R.sup.2                                                                          R.sup.3                                                                          R.sup.6                                                                          R.sup.7                                                                          DATA                                         __________________________________________________________________________    78                                                                                     ##STR127##  CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         mpt. 103-105° C.                      79                                                                                     ##STR128##  CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         mpt. 90-93° C.                        80                                                                                     ##STR129##  CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          ##STR130##                                  81                                                                                     ##STR131##  CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         Oil ir (nujol) 1720, 1670, 1560                                               cm.sup.-1                                    82                                                                                     ##STR132##  CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         mpt. 90-93° C.                        __________________________________________________________________________

Compounds of formula (I) can be prepared by rearrangement of a compoundof formula (II): ##STR133## wherein R¹, X, X¹, X² and Y are as definedin relation to formula (I) in the presence of a cyanide source and amoderate base.

The reaction is suitably carried out in an inert organic solvent such asacetonitrile and at a temperature of from -30° C. to 90° C., preferablyat from 20° C.-40° C.

Suitable cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself.

A preferred cyanide source is acetone cyanohydrin.

The amount of the cyanide source employed is sufficient to catalyse thereaction, for example from 1-50 mole percent of the compound of formula(II), preferably from 1 to 10 mole percent.

Moderate bases suitable for use in this reaction include both organicbases such as tertiary amines and inorganic bases such as alkali metalcarbonates and phosphates. Suitable tertiary amines includetrialkylamines such as triethylamine, trialkanolamines such astriethanolamine, and pyridine. Suitable inorganic bases includepotassium carbonate and trisodium phosphate.

Suitably the base is used in an amount of from about 1 to about 4 molesper mole of compound of formula (II), preferably about 2 moles per mole.

Compounds of formula (II) can be prepared by reacting a compound offormula (III): ##STR134## wherein X¹, X², and Y are as defined inrelation to formula (I) with a compound of formula (IV):

    R.sup.1 CXZ                                                (IV)

wherein R¹ and X are as defined in relation to formula (I) and Z is aleaving group, in the presence of a base.

Suitable bases for use in the reaction are the moderate bases describedabove for use in the rearrangement of the compound of formula (II). Apreferred base is triethylamine.

Suitable leaving groups Z include halide such as chloride.

The reaction is suitably carried out in an inert organic solvent such asdichloromethane, 1,2-dichloroethane, toluene, acetonitrile, ordimethylformamide at moderate temperatures of from 0° C. to 50° C.,conveniently at room temperature.

Compounds of formula (II) may also be prepared by reacting a compound offormula (III) with an acid of formula (V):

    R.sup.1 CXOH                                               (V)

wherein R¹ and X are as defined in relation to formula (I), in thepresence of a dehydrating agent and a basic organic catalyst.

Suitable dehydrating agents include dicyclohexyl-carbodiimide (DCC)which is employed in an amount of at least one molar equivalent to thecompounds of formulae (III) and (V).

Examples of suitable basic organic catalysts include4-dimethylaminopyridine (DMAP) and 4-pyrrolidinopyridine (PPY).

The reaction is suitably carried out in an inert organic solvent such asacetonitrile, tetrahydrofuran, dichloromethane or 1,2-dichloroethane.Moderate temperatures for example from 0° C. to 40° C. can be employed,conveniently ambient temperature.

Alternatively a compound of formula (I) can be prepared by reacting acompound of formula (III) as hereinbefore defined with a compound offormula (VI):

    R.sup.1 CXCN                                               (VI)

wherein R¹ and X are as hereinbefore defined, in the presence of a baseand a Lewis acid.

Suitable bases are the moderate bases described above for use in therearrangement of the compound of formula (II).

Suitable Lewis acids are zinc chloride and aluminium trichloride,preferably zinc chloride.

The reaction is carried out in an organic solvent such as acetonitrileor methylene chloride and at moderate temperatures of from -20° C. to+40° C.

Suitably both the zinc chloride and the base are present in a slightmolar excess with respect to the compounds of formula (III) and (VI).

Compounds of formulae (III), (IV), (V) and (VI) are either knowncompounds or they can be prepared from known compounds by conventionalmethods.

For instance a particular example of a compound of formula (V) arecompounds of formula (VA) ##STR135## wherein R⁵ and R⁶ are as definedabove.

These compounds can be prepared as set out in Scheme A. ##STR136##

Suitable conditions for the first stage in Scheme A are found in anarticle, see R Jones JACS, 73 3686.

Conditions from the two subsequent steps are outlined in GB 2,149,402A.

A particular example of a compound of formula (III) is a compound offormula (IIIA): ##STR137##

Compounds of formula (IIIA) wherein R¹⁶, R¹⁷, R²⁰ and R²¹ are methyl orhydrogen and their preparation are described by Riedl and Risse (JustusLiebigs Annalen der Chemie, 1954, 585, 209).

Compounds of formula (IIIA) wherein R¹⁶, R17, R²⁰ and R²¹ are the sameand are C₁₋₄ alkyl can be prepared by the following reaction Scheme B.##STR138## wherein X' is a leaving group such as halide, in particulariodide. Suitable reaction conditions will be apparent by analogy withthe above-mentioned publication, For example, one suitable base for usein the first step in Scheme B is sodium methoxide in methanol. Asuitable acid for use in second step of Scheme B is an inorganic acidsuch as hydrochloric acid.

By adjusting the conditions in the first step of the process, it may bepossible to obtain compounds of formula (IIIA) wherein R²⁰ and/or R²¹are hydrogen.

Alternatively compounds of formula (IIIA) can be prepared using themethods described by Murin et al (Chem. Bet. 1959, 92, 2033) or methodsanalogous thereto.

In this way compounds of formula (IIIA) are prepared by cyclisation of acompound of formula (VII): ##STR139## in the presence of a base such assodium methoxide an organic solvent such as methanol. Compounds offormula (VII) can be prepared as outlined in Scheme C. ##STR140##

Precise reaction conditions for each step in Scheme B will depend uponthe particular compounds involved and can be determined by routineprocedures and the relevant literature.

Compounds of formula (VIII) can be prepared by the reaction of compoundsof formula (IX): ##STR141## with a compound of formula R²⁰ X' andoptionally thereafter with a compound of formula R²¹ X' in the presenceof a base such as sodium methoxide in an organic solvent such asmethanol, wherein R²⁰, R²¹ and X' are as hereinbefore defined.

When R²⁰ and R²¹ are the same, then the reaction can be carried out in asingle step. By controlling the reaction conditions, the extent of thereaction (i.e. whether one or both hydrogen atoms on the methylene arereplaced by R²⁰) can be determined.

Compounds of formula (IX) can be prepared by reaction of a compound offormula (X): ##STR142## wherein R¹⁶ and R¹⁷ are as hereinbefore defined,with (a) a strong base such as lithium diisopropyl-amide and (b) CH₃ O₂CCl under conventional reaction conditions.

Compounds of formula (X) can be prepared by reacting a compound offormula (XI): ##STR143## with a compound of formula R¹⁶ X' in thepresence of a base; and optionally thereafter R¹⁷ X' wherein R¹⁶, R¹⁷and X' are hereinbefore defined, as described above for the reaction ofthe compound of formula (IX).

Alternatively compounds of formula (IA) can be prepared by reacting acompound of formula (VIIIA) as set out in Scheme C with a compound offormula (XII): ##STR144## wherein R¹ is as hereinbefore defined, in thepresence of aluminium trichloride.

Reactions of this type are described by Merenyi and Nilson (Acta Chem.Scand, 1963, 17, 1801 and Acta Chem. Scand, 1964, 18, 1368).

Compounds of formula (XII) are known compounds or they can be preparedfrom known compounds by conventional methods.

Furthermore, compounds of formula (IA) wherein R¹⁶, R¹⁷, R²⁰ and R²¹ arethe same, can also be prepared by reacting a compound of formula (XIII):##STR145## with a compound of formula R¹⁶ X' in the presence of a base,wherein R¹, R¹⁶ and X' are as hereinbefore defined.

Suitable bases for use in the reaction are strong bases such as sodiummethoxide.

The reaction is suitably carried out in an organic solvent such asmethanol at temperatures of from 0° to 100° C.

The compounds of formula (I) are active as herbicides and therefore, ina further aspect the invention provides a process for severely damagingor killing unwanted plants which process comprises applying to theplants, or to the growth medium of the plants, an effective amount of acompound of formula (I) as hereinbefore defined.

The compounds of formula (I) are active against a broad range of weedspecies including monocotyledenous and dicotyledonous species. They mayshow some selectivity towards certain species, in particular maize.

The compounds of formula (I) may be applied directly to the plant(post-emergence application) or to the soil before the emergence of theplant (pre-emergence application).

The compounds of formulae (I) may be used on their own to inhibit thegrowth of, severely damage, or kill plants but are preferably used inthe form of a composition comprising a compound of the invention inadmixture with a carrier comprising a solid or liquid diluent.

Therefore, in yet a further aspect the invention provides plant growthinhibiting, plant damaging, or plant killing compositions comprising acompound of formula (I) as hereinbefore defined and an inert carrier ordiluent.

Compositions containing compounds of formula (I) include both dilutecompositions, which are ready for immediate use, and concentratedcompositions, which require to be diluted before use, usually withwater. Preferably the compositions contain from 0.01% to 90% by weightof the active ingredient. Dilute compositions ready for use preferablycontain from 0.01 to 2% of active ingredient, while concentratedcompositions may contain from 20 to 90% of active ingredient, althoughfrom 20 to 70% is usually preferred.

The solid compositions may be in the form of granules, or dustingpowders wherein the active ingredient is mixed with a finely dividedsolid diluent, e.g., kaolin, bentonire, kieselguhr, dolomite, calciumcarbonate, talc, powdered magnesia, Fuller's earth and gypsum. They mayalso be in the form of dispersible powders or grains, comprising awetting agent to facilitate the dispersion of the powder or grains inliquid. Solid compositions in the form of a powder may be applied asfoliar dusts.

Liquid compositions may comprise a solution or dispersion of an activeingredient in water optionally containing a surface-active agent, or maycomprise a solution or dispersion of an active ingredient in awater-immiscible organic solvent which is dispersed as droplets inwater.

Surface-active agents may be of the cationic, anionic, or non-ionictype. The cationic agents are, for example, quaternary ammoniumcompounds (e.g. cetyltrimethylammonium bromide). Suitable anionic agentsare soaps; salts or aliphatic mono ester of sulphuric acid, for examplesodium lauryl sulphate; and salts of sulphonated aromatic compounds, forexample sodium dodecylbenzenesulphonate, sodium, calcium, and ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of thesodium salts of diisopropyl and triisopropylnaphthalenesulphonic acid.Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, orwith alkylphenols such as octyl- or nonyl-phenol or octyl-cresol. Othernon-ionic agents are the partial esters derived from long chain fattyacids and hexitol anhydrides, for example sorbitan monolaurate; thecondensation products of the partial ester with ethylene oxide; and thelecithins.

The aqueous solutions or dispersions may be prepared by dissolving theactive ingredient in water or an organic solvent optionally containingwetting or dispersing agent(s) and then, when organic solvents are used,adding the mixture so obtained to water optionally containing wetting ordispersing agent(s). Suitable organic solvents include, for example,ethylene di-chloride, isopropyl alcohol, propylene glycol, diacetonealcohol, toluene, kerosene, methylnaphthalene, the xylenes andtrichloroethylene.

The compositions for use in the form of aqueous solutions or dispersionsare generally supplied in the form of a concentrate containing a highproportion of the active ingredient, and the concentrate is then dilutedwith water before use. The concentrates are usually required towithstand storage for prolonged periods and after such storage, to becapable of dilution with water to form aqueous preparations which remainhomogeneous for a sufficient time to enable them to be applied byconventional spray equipment. Concentrates conveniently contain 20-90%,preferably 20-70%, by weight of the active ingredient(s). Dilutepreparations ready for use may contain varying amounts of the activeingredient(s) depending upon the intended purpose; amounts of 0.01% to10.0% and preferably 0.1% to 2%, by weight of active ingredient(s) arenormally used.

A preferred form of concentrated composition comprising the activeingredient which has been finely divided and which has been dispersed inwater in the presence of a surface-active agent and a suspending agent.Suitable suspending agents are hydrophilic colloids and include, forexample, polyvinylpyrrolidone and sodium carboxymethylcellulose, and thevegetable gums, for example gum acacia and gum tragacanth. Preferredsuspending agents are those which impart thixotropic properties too, andincrease the viscosity of the concentrate. Examples of preferredsuspending agents include hydrated colloidal mineral silicates, such asmontmorillonite, heidellite, nontronite, hectorite, saponite, andsaucorite. Bentonite is especially preferred. Other suspending agentsinclude cellulose derivatives and polyvinyl alcohol.

The rate of application of the compounds of the invention will depend ona number of factors including, for example, the compound chosen for use,the identity of the plants whose growth is to be inhibited, theformulations selected for use and whether the compound is to be appliedfor foliage or root uptake. As a general guide, however, an applicationrate of from 0.005 to 20 kilograms per hectare is suitable while from0.1 to 10 kilograms per hectare may be preferred.

The compositions of the invention may comprise, in addition to one ormore compounds of the invention, one or more compounds not of theinvention but which possess biological activity. Accordingly in yet astill further embodiment the invention provides a herbicidal compositioncomprising a mixture of at least one herbicidal compound of formula (I)as hereinbefore defined with at least one other herbicide.

The other herbicide may be any herbicide not having the formula (I). Itwill generally be a herbicide having a complementary action in theparticular application. For example it may be desirable in certaincircumstances to use the compound of formula (I) in admixture with acontact herbicide.

Examples of useful complementary herbicides include:

A. benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as3-isopropylbenzo-2,1,3-thiadiazin-4-one-2,2-dioxide (bentazon);

B. hormone herbicides, particularly the phenoxy alkanoic acids such as4-chloro-2-methylphenoxy acetic acid (MCPA),2-(2,4-dichloropbenoxy)propionic acid (dichlorprop),2,4,5-trichlorophenoxyacetic acid (2,4,5-T),4-(4-chloro-2-methylphenoxy)butyric acid (MCPB),2,4-dichlorophenoxyacetic acid (2,4-D), 4-(2,4-dichlorophenoxy)butyricacid (2,4-DB), 2-(4-chloro-2-methylphenoxy)propionic acid (mecoprop),and their derivatives (e.g. salts, esters and amides);

C. 3-[4-(4-halophenoxy)phenyl]-1,1-dialkylureas such as3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea.

D. Dinitrophenols and their derivatives (e.g. acetates) such as2-methyl-4,6-dinitrophenol (DNOC), 2-t-butyl-4,6-dinitrophenol(dinoterb), 2-secbutyl-4,6-dinitrophenol (dinoseb) and its ester,dinoseb acetate;

E. dinitroaniline herbicides such asN',N'-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine(dinitramine), 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline(trifluralin) and 4-methylsulphonyl-2,6-dinitro-N,N-dipropylaniline(nittalin);

F. phenylurea herbicides such asN'-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron) andN,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (flumeturon);

G. phenylcarbamoyloxyphenylcarbamates such as 3-[methoxycarbonylamino]phenyl (3-methylphenyl)carbamate (phenmedipham) and3-[ethoxycarbonylamino]phenyl phenylcarbamate (desmedipham);

H. 2-phenylpyridazin-3-ones such as5-amino-4-chloro-2-phenylpyridazin-3-one (pyrazon);

I. uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil(lenacil), 5-bromo-3-sec-butyl-6-methyl-uracil (bromacil) and3-t-butyl-5-chloro-6-methyl-uracil (terbacil);

J. triazine herbicides such as2-chloro-4-ethylamino-6-(i-propylamino)-1,3,5-triazine (atrazine),2-chloro-4,6-di(ethylamino)-1,3,5-triazine (simazine) and2-azido-4-(i-propylamino)-6-methylthio-1,3,5-triazine (aziprotryne);

K. 1-alkoxy-l-alkyl-3-phenylurea herbicides such as3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linuron),3-(4-chlorophenyl)-1-methoxy-1-methylurea (monolinuron),3-(4-bromo-4-chlorophenyl)-1-methoxy -1-methylurea (chlorobromuron).

L. thiolcarbamate herbicides such as S-propyl dipropylthiocarbamate(vernolate);

M. 1,2,4-triazin-5-one herbicides such as4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazine-5-one (metamitron)and 4-amino-6-t-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one(metribuzin);

N. benzoic acid herbicides such as 2,3,6-trichlorobenzoic acid(2,3,6-TBA), 3,6-dichloro-2-methoxybenzoic acid (dicamba) and3-amino-2,5-dichlorobenzoic acid (chloramben);

O. anilide herbicides such asN-butoxymethyl-chloro-2',6'-diethylacetanilide (butachlor), thecorresponding N-methoxy compound (alachlor), the correspondingN-i-propyl compound (propachlor), 3',4'-dichloropropionanilide(propanil) and 2-chloro-N-[pyrazol-1-ylmethyl]acet-2'-6'-xylidide(metazachlor);

P. dihalobenzonitrile herbicides such as 2,6-dichlorobenzonitrile(dichlobenil), 3,5-dibromo-4-hydroxybenzonitrile (bromoxynil) and3,5-diiodo-4-hydroxybenzonitrile (ioxynil);

Q. haloalkanoic herbicides such as 2,2-dichloropropionic acid (dalapon),trichloroacetic acid (TCA) and salts thereof;

R. diphenylether herbicides such as 4-nitrophenyl2-nitro-4-trifluoromethylphenyl ether (fluorodifen), methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate (befenox),2-nitro-5-(2-chloro-4-trifluoromethylphenoxy) benzoic acid (acifluorfen)and salts and esters thereof, 2-chloro-4-trifluoromethylphenyl3-ethoxy-4-nitrophenyl ether (oxyfluorfen) and5-(2-chloro-4-(trifluoromethyl)phenoxy)-N-(methylsulfonyl)-2-nitrobenzamide (fomesafen); and

S. phenoxyphenoxypropionate herbicides such as2-(4-(4'-trifluoromethylphenoxy)-phenoxy)-propionic acid methylester(trifop-methyl),2-(4-((5-trifluoromethyl)-2-(pyridinyl)oxy)phenoxypropanoic acid(fluazifop) and esters thereof, 2-(4-((3-chloro-5-trifluoromethyl)-2-pyridinyl)oxy)phenoxy)propanoic acid (haloxyfop) and esters thereof,2-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxypropanoic acid (xylofop) andesters thereof; and

T. cyclohexanedione herbicides such as2,2-dimethyl-4,6-dioxo-5-(1-((2-propenyloxy)amino)-butylidine)cyclohexane carboxylic acid (alloxydim) and salts thereof,2-(1-ethoxyimino)butyl-5-(2-(ethylthio)-propyl)-3-hydroxy-2-cyclohexen-1-one(sethoxydim), 2-(1-(3-chloroallyloxyimino)butyl)-5-(2-ethylthio-propyl)-3-hydroxy cyclohex-2-enone (cloproxydim),(1-ethoxyimino)butyl)-3-hydroxy-5-thian-3-yl cyclohex-2-enone(cycloxydim); and

U. sulfonyl urea herbicides such as2-chloro-N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl)benzenesulphonamide (chlorosulfuron), methyl 2-((((4,6-dimethyl-2-pyrimidinyl)amino)carbonyl)amino)sulphonylbenzoic acid (sulfometuron),2-(((3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbonyl)amino)sulphonyl)benzoicacid (metsulfuron) and esters thereof;

V. imidazolidinone herbicides such as2-(4,5-dihydro-4-isopropyl-4-methyl-5-oxoimidazol-2-yl)quinoline-3-carboxylicacid (imazaquin), methyl6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluate and p-toluateisomer (AC 222293)

W. arylanilide herbicides such as1-methylethyl-N-benzoyl-N-(3-chloro-4-fluorophenyl)-L-alanine(flamprop-isopropyl), ethylN-benzoyl-N-(3,4-dichloro-phenyl)-DL-alaninate (benzoylprop-ethyl),N-(2,4-difluorophenyl)-2-(3-(trifluoromethyl)phenoxy)-3-pyridinecarboxamide(diflufenican); and

X. amino acid herbicides such as N-(phosphonomethyl)glycine (glyphosate)and DL-homoalanin-4-yl(methyl)phosphinic acid (phosphinothricin) andtheir salts and esters; and

Y. organoarsenical herbicides such as monosodium methanearsonate (MSMA);and

Z. miscellaneous herbicides including N,N-dimethyldiphenylacetamide(diphenamid), N-(1-naphthyl)phthalamic acid (naptalam) and3-amino-1,2,4triazole, 2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuranmethanesulfonate (ethofumesate), 7-oxabicyclo (2.2.1) heptane.1-Methyl-4-(1-methylethyl)-2-(2-methyl-phenylmethoxy)-exo (cinmethylin);

AA. Examples of useful contact herbicides include:

bipyridylium herbicides such as those in which the active entity is the1,1'-dimethyl-4,4'-dipyridylium ion (paraquat) and those in which theactive entity is the 1,1'-ethylene-2,2'-dipyridylium ion (diquat);

The following Examples illustrate the preparation of representativecompounds of the invention.

EXAMPLE 1

This Example illustrates the preparation of Compound No. 1 in Table I.

To 2-thiophenecarboxylic acid chloride (1.2 ml) in dry dichloromethane(50 ml) was added Dimedone (1.57 g) and triethylamine (1.7 ml) dropwise.The reaction mixture was stirred at room temperature for 11/2 hours andthen evaporated to dryness to yield a soft solid (4.83 g). Dryacetonitrile (35 ml) was added to the solid which dissolved to form ayellow solution. Triethylamine (3.2 ml) and acetone cyanohydrin (6drops) were added to the solution which was then stirred at roomtemperature for 2 hours. On purification by column chromatography usinga silica column with an eluent consisting of hexane 50: ethyl acetate50: acetic acid 1, the main orange band was collected and crystallisedon standing to Compound No. 1 (97% yield).

EXAMPLE 2

This Example illustrates the preparation of Compound No. 2 in Table I.

A mixture of 2,5-dichlorothiophene acid chloride (1.06 g) and Dimedone(0.70 g) in dry acetonitrile (25 ml) was cooled in a water bath andtriethylamine (0.76 ml) and acetonitrile (5 ml) added dropwise. Themixture was stirred at room temperature for 1/2 hour, triethylamine (1.4ml) and acetonecyanohydrin (4 drops) added and stirring was continuedfor 20 hours, after which the solution was evaporated to dryness.

The residue was dissolved in ethyl acetate and the solution applied to asilica column using a eluent of hexane 50: ethylacetate 50: acetic acid1 and the main orange band collected and solidified.

Further purification by recrystallisation from hexane and columnchromatography as described above yielded Compound No. 2 (0.24 g).

EXAMPLE 3

This Example illustrates the preparation of Compound No. 5 in Table I.

5-Bromo-2-thiophenecarboxylic acid (2.09 g), dry dichloroethane (30 ml)and thionyl chloride (0.75 ml) were heated together at 80° C. for 4hours. The mixture was cooled in an ice water Oath and Dimedone (1.40 g)added followed by the dropwise addition of triethylamine (2.8 ml) in drydichloroethane (5 ml). After 1 hour at room temperature furthertriethylamine (2.8 ml) and acetonecyanohydrin (6 drops) were added andstirring continued for 15 hours. The solution was then left for a totalof 3 days at room temperature, after which time it was evaporated todryness, the residue dissolved in ethylacetate and the resultingsuspension applied to a silica column and eluted with hexane 50:ethylacetate 50: acetic acid 1 and the main orange band collected whichsolidified to give Compound No. 5 as an orange solid (1.26 g).

EXAMPLE 4

This Example illustrates the preparation of Compound No. 6 in Table I.

5-Methyl-2-thiophenecarboxylic acid (0.71 g), cyclohexan-1,3-dione (0.5g) and a small amount of (4-dimethylaminopyridine) (100 mgs) weredissolved in dry dichloromethane (20 ml) at 15° C. anddicyclohexylcarbodiimide (1.02 g) added. The reaction mixture wasstirred at 18°-20° C. for 3-4 hours and then filtered and evaporated. Tothe resulting oil were added dry acetonitrile (8 ml), acetonecyanohydrin (4 drops) and triethylamine (1.4 ml) and the mixture stirredfor 2-3 hours at room temperature and subsequently evaporated todryness.

The residue was purified by column chromatography using as eluent,hexane 70: ethylacetate 30: acetic acid 3 and the main yellow bandcollected and evaporated to give Compound No. 6 as a cream solid (0.38g).

EXAMPLE 5

This Example illustrates the preparation of compound 10 in Table 1.

5-Chloro-2-thienoyl chloride (8.0 g, 44 mmol) and 1.3-cyclohexanedione(5.0 g, 44 mmol) were dissolved in 150 ml of methylene chloride.Triethylamine (15 ml, 110 mmol) was added and the resulting mixture wasstirred at room temperature for fifteen minutes. The solution was washedwith dilute hydrochloric acid, 5% potassium carbonate and saturatedsodium chloride, dried over anhydrous magnesium sulfate and concentratedin vacuum. The residue was dissolved in 100 ml of acetonitrile.Triethylamine (15 ml, 110 mmol) and acetone cyanohydrin (0.2 g) wereadded and the mixture stirred at room temperature for 2 hours. Afterdilution with ether, the solution was washed with dilute hydrochloricacid and extracted with 5% potassium carbonate. The basic extract wasacidified with hydrochloric acid and extracted with ether. The etherextract was washed with saturated sodium chloride, dried over magnesiumsulfate and concentrated in vacuum yielding 3.8 g of the desired product(mp. 31°-35° C.). It was identified as such by nuclear magneticresonance spectroscopy, infrared spectroscopy and mass spectroscopy.

EXAMPLE 6

This Example illustrates the preparation of compound 42 in Table 1.

4-Carboxy-1-methyl-5-trifluoromethyl-1H-pyrazole (5.0 g, 26 mmol) wasdissolved in a mixture of tetrahydrofuran (25 ml) and acetonitrile (25ml). Dicyclohexylcarbodiimide (5.3 g, 26 mmol) was added and theresulting mixture was stirred at room temperature for 5 minutes.1,3-Cyclohexanedione (2.9 g, 26 mmol) dissolved in a mixture oftetrahydrofuran (25 ml) and acetonitrile (25 ml) was added and themixture stirred at room temperature overnight. The reaction mixture wasfiltered and the filtrate was concentrated in vacuum. The residue wasdissolved in acetonitrile (100 ml). Triethylamine (9 ml, 66 mmol) andtrimethylsilyl cyanide (0.2 g) were added and the mixture stirred at 50°C. for 4 hours. After dilution with ether, the solution was washed withdilute hydrochloric acid and extracted with 5% potassium carbonate. Thebasic extract was acidified with hydrochloric acid and extracted withether. The ether extract was washed with saturated sodium chloride,dried over anhydrous magnesium sulfate and concentrated in vacuumyielding 2.7 g of the desired product as a yellow solid (mp. 118°-122°C.). It was identified as such by nuclear magnetic resonancespectroscopy, infrared spectroscopy and mass spectroscopy.

Compounds 7-71 and 78 were prepared by methods analogous to thoseemployed in Examples 5 or 6.

EXAMPLE 7

This Example illustrates the preparation of compound 79 in Table II.##STR146##

The ester (i) (4.17 g was dissolved in isopropylalcohol (50 ml) andsodium hydroxide (0.77 g) in water (5 ml) added with stirring. Themixture was heated under reflux for 2 hours, and then poured into 2Maqueous hydrochloric acid to quench the reaction. The product was thenextracted into ethyl acetate and the extracts dried over magnesiumsulphate. Concentration under reduced pressure gave the acid (ii) as ayellow solid.

Step b

2,2,4,4-Tetramethyl-cyclohexan-1,3,5-trione (0.50 g) and the acid fromstep (a)) (0.58 g) were stirred together in dry dichloromethane DMAP (ca50 mg) and dicyclohexyl carbodiimide (0.47 g) were added and the mixturewas allowed to stand to room temperature overnight. The reaction mixturewas filtered and concentrated under reduced pressure to give a yellowsolid. This solid was dissolved in acetonitrile and triethylamine (0.76ml) added. Acetone cyanohydrin (4 drops) were added and the mixturestirred at room temperature for 5 hours. It was then poured into 2Maqueous hydrochloric acid, extracted with ethyl acetate, dried andconcentrated under reduced pressure and recrystallised fromethanol/ethyl acetate to give compound 78 as a yellow crystalline solid(0.15 g).

EXAMPLE 8

This Example illustrates the preparation of compound 80 in Table 2.

Step a

Ethyl 2,4-dimethylthiazole-5-carboxylate (3.0 g, 0.016 mol) wasdissolved in isopropyl alcohol (50 ml) and sodium hydroxide (0.71 g,0.018 mol) in H₂ O (5 ml) added. The reaction mixture was stirred atroom temperature for 1 hour then heated under reflux for 1 hour, pouredinto H₂ O, acidified with 2M hydrochloric acid solution extracted withethyl acetate. The aqueous phase was concentrated under reducedpressure, triturated with water, and filtered to give a pale pink solid(mpt. 200° C.).

Step b

2,2,4,4-Tetramethylcyclohexan-1,3,5-trione (0.50 g, 2.75 mmol) wasdissolved in dichloromethane (30 ml) and the product from step (a), andDMAP (ca 50 mg) and dicyclohexylcarbodiimide (0.47 g) added. Thereaction mixture was stirred at room temperature for 1 hour, and thenfiltered and concentrated under reduced pressure. The residue wasdissolved in acetonitrile (30 ml) and triethylamine (0.76 ml) was added,together with acetone cyanohydrin (4 drops). The reaction mixture wasstirred at room temperature for 2 hours and then heated under reflux for11/2 hours. Reaction mixture was then poured into 2M aqueoushydrochloric acid solution, extracted with ethyl acetate, dried andconcentrated under reduced pressure to give a yellow oil and solid whichwas triturated repeatedly with CH₂ Cl₂ to remove triketone startingmaterial. Compound 80 was obtained as a yellow oil.

Compounds 72 and 83 were prepared by methods analogous to thosedescribed in Examples 7 and 8.

EXAMPLE 9

This Example illustrates the preparation of compound 80 in Table II.

Step a

5-(2-Pyridyl)thiophene-2-carboxylic acid (1.0 g) was stirred in toluene(50 ml) and dimethylformamide (3 drops). Thionyl chloride (1.6 ml, 9.76mmol) was added and the reaction mixture stirred at room temperature for6 hours, then heated under reflux for 1 hour and filtered. Concentrationunder reduced pressure gave a yellow solid (1.08 g).

Step b

Compound (iii) (0.50 g) and the acid chloride from step (a) (0.63 g),were stirred in dry acetonitrile (15 ml) at room temperature.Triethylamine (0.38 ml) was added, the cloudy yellow suspension changingto clear orange then to clear dark yellow as the triethylamine wasadded. The reaction mixture was then stirred at room temperature for 2hours and triethylamine (0.76 ml) and acetone cyanohydrin (4 drops) wereadded. After stirring at room temperature for 6 hours the reactionmixture was poured into H₂ O (50 ml), acidified with 2M HCl (100 ml),extracted with EtOAc (100 ml), the EtOAc phase was washed with 50% NA₂CO₃ solution (100 ml) and the base layer then acidified with 2M HCl. Themixture was then extracted with CH₂ Cl₂, and the CH₂ Cl₂ phase washedwith brine (25 ml), dried over MgSO₄, filtered and concentrated underreduced pressure to give a bright yellow solid.

Compound 81 was obtained by prep plate chromatography using the solventsystem ethylacetate/hexane/acetic acid in the ratio 75:175:1. It wasobtained as a yellow oil that crystallised on standing.

Compounds 73, 74, 75 and 76 were prepared by methods analogous to thosedescribed in Example 9.

EXAMPLE 10

This Example illustrates the preparation of compound 77. ##STR147##

The salt (v) (0.84 g) was treated with toluene (35 ml) and DMF (5 drops)added. The stirred suspension was treated dropwise with oxalyl chloride(0.75 ml). This caused a colour change to purple and considerableeffervescence. The mixture was stirred overnight at room temperature andthen evaporated under reduced pressure to give an off white solid. Thiswas treated with acetonitrile (15 ml) and partially dissolved. Themixture was stirred with ice-bath cooling and cyclohexane-1,3-dione (0.6g) was added. Triethylamine (0.75 ml) was then added dropwise. Most ofthe precipitate dissolved. The mixture was stirred with continuedcooling for 3 horus. Allowed to obtain room temperature and then treatedwith acetone cyanohydrin (6 drops). Triethylamine (1.8 ml) was thenslowly added.

The mixture was then stirred at room temperature for 4 hours then leftto stand over the weekend. A yellow and orange solution resulted. Thiswas filtered and the filtrate poured into water (100 mls). The resultingalkaline solution was acidified with dilute HCl and became cloudy.

The mixture was extracted with dichloromethane to give a yellow organiclayer. This was extracted with sodium carbonate solution and the aqueouslayer acidified with dilute hydrochloric acid. The cloudy mixture formedwas extracted with dichloromethane and the organic phase washed withwater dried over magnesium sulphate and then filtered and evaporated togive a yellow oil which set on standing to give compound 77 as a yellowsolid (0.59).

Biological Data

As previously mentioned, the herein described compounds produced in theabove-described manner are phytotoxic compounds which are useful andvaluable in controlling various plant species. Selected compounds ofthis invention were tested as herbicides in the following manner.

Pre-emergence herbicide test. On the day preceding treatment, seeds ofseven different weed species are planted in loamy sand soil inindividual rows using one species per row across the width of a flat.The seeds used are green foxtail (FT) (Setaria viridis), watergrass (WG)(Echinochloa crusgalli), wild oat (WO) (Arena fatua), annualmorningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutliontheophrasti), Indian mustard (MD) (Brassica juncea), and yellow nutsedge(YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to40 seedlings per row, after emergence, depending upon the size of theplants.

Using an analytical balance, 600 milligrams (mg) of the compound to betested are weighed out on a piece of glassine weighing paper. The paperand compound are placed in a 60 milliliter (ml) wide-mouth clear bottleand dissolved in 45 ml of acetone or substituted solvent. Eighteen ml ofthis solution are transferred to a 60 ml wide-mouth clear bottle anddiluted with 22 ml of a water and acetone mixture (19:1) containingenough polyoxyethylene sorbitan monolaurate emulsifier to give a finalsolution of 0.5% (v/v). The solution is then sprayed on a seed flat on alinear spray table calibrated to deliver 80 gallons per acre (748 L/ha).The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats ace placed in the greenhouse at a temperatureof 70° to 80° F. and watered by sprinkling. Two weeks after treatment,the degree of injury or control is determined by comparison withuntreated check plants of the same age. The injury rating from 0 to 100%is recorded for each species as percent control with 0% representing noinjury and 100% representing complete control.

Post Emergence Test

Post emergence results were obtained using similar methods except thatthe compounds were applied to the young plants.

The results of the tests are shown in the following Tables III and IV.

                  TABLE III                                                       ______________________________________                                                 Pre-emergence Herbicidal Activity                                    Compound Application Rate 4.00 lb/ac                                          No.      FT     WG     WO   AMG   VL    MD   YNG                              ______________________________________                                        4        0      0      0    0     100   10   35                               6        25     20     0    0     0     0    0                                7        8      0      5    0     10    70   70                               11       20     0      0    0     25    60   0                                12       20     25     0    0     0     25   0                                14       0      0      0    5     0     20   0                                16       0      0      0    0     85    25   70                               18       50     35     0    0     100   10   0                                19       60     0      0    0     20    100  25                               20       30     25     0    25    100   95   30                               21       0      0      0    0     100   100  30                               22       0      --     25   0     0     0    0                                23       25     40     20   0     0     0    0                                29       70     100    95   30    95    100  80                               30       100    100    80   85    100   100  80                               31       0      10     0    0     10    40   80                               32       0      0      0    0     0     0    80                               33       0      0      0    0     0     0    30                               35       0      30     0    0     30    0    30                               36       0      0      30   80    90    10   0                                37       30     0      0    0     0     0    0                                38       0      0      0    0     5     0    0                                40       80     50     30   10    50    50   70                               41       90     100    20   30    100   95   80                               42       100    50     100  100   100   95   80                               43       90     30     90   100   100   60   80                               44       90     85     20   100   100   5    80                               45       100    100    20   100   100   90   80                               46       20     85     20   100   100   60   80                               47       30     80     0    100   100   80   80                               48       80     80     0    100   100   20   70                               49       100    20     100  100   100   90   80                               50       60     90     0    100   100   95   80                               51       100    90     30   100   100   40   30                               52       100    95     60   100   90    75   70                               53       80     70     20   100   100   10   0                                54       100    80     20   100   60    100  0                                55       100    70     30   98    90    85   20                               56       95     70     20   80    95    75   60                               57       100    90     20   95    95    75   80                               60       20     25     0    0     0     0    0                                65       30     0      0    0     0     0    0                                66       0      --     25   0     0     0    0                                69       25     40     20   0     0     0    0                                78       100    100    90   100   90    90   80                               ______________________________________                                    

Compounds 13, 15, 24, 25, 26, 27, 28, 34, 39 showed no pre-emergenceactivity against the test species at the given rate of application.

                  TABLE IV                                                        ______________________________________                                                 Post-emergence Herbicidal Activity                                   Compound Application Rate 4.00 lb/ac                                          No.      FT     WG     WO   AMG   VL    MD   YNG                              ______________________________________                                        4        40     25     0    85    100   100  40                               6        20     30     0    25    70    50   0                                7        0      30     0    10    0     10   0                                9        40     30     10   0     100   95   0                                10       0      30     0    0     0     40   0                                11       20     30     0    35    20    30   0                                12       0      0      0    0     25    25   0                                13       10     20     0    0     15    25   0                                14       0      0      0    15    0     20   0                                15       0      0      0    20    20    80   0                                16       0      0      0    0     60    100  80                               18       0      20     10   100   100   90   35                               19       0      0      0    25    60    100  70                               20       20     0      0    25    100   100  0                                21       0      25     0    40    70    80   0                                22       0      20     0    0     0     35   0                                24       20     0      --   30    20    40   0                                25       20     25     0    0     35    50   15                               26       0      0      0    0     0     0    20                               28       0      40     0    20    40    80   0                                29       65     80     80   10    90    80   50                               30       80     80     40   30    30    50   80                               31       0      50     0    5     80    80   60                               32       0      0      0    0     50    50   30                               33       0      0      0    5     30    0    10                               35       0      30     0    0     10    10   0                                36       10     10     80   100   100   100  70                               40       80     50     30   10    50    50   70                               41       60     90     80   20    100   80   70                               42       100    90     80   100   100   90   80                               43       90     85     50   100   100   100  70                               44       10     20     10   10    90    80   30                               45       85     90     90   100   90    90   75                               46       20     40     10   90    80    20   70                               47       10     40     0    80    80    60   70                               48       5      40     0    100   95    30   60                               49       30     70     5    60    60    20   80                               50       20     60     5    60    60    40   80                               51       30     40     20   80    100   25   0                                52       50     60     50   85    90    40   30                               53       10     10     0    80    80    5    0                                54       10     30     10   60    60    10   0                                55       40     50     30   50    30    40   10                               56       20     50     40   60    80    20   30                               57       50     50     50   80    80    40   40                               58       40     30     10   0     100   95   0                                60       20     30     0    25    70    80   0                                61       0      0      0    0     25    25   0                                62       10     20     0    0     15    25   0                                63       0      0      0    15    0     20   0                                64       0      0      0    20    20    50   0                                66       0      0      0    0     5     0    0                                70       40     35     20   15    70    60   20                               71       50     60     0    15    10    40   10                               78       85     80     80   80    85    70   80                               ______________________________________                                    

GLASSHOUSE TESTS FOR HERBICIDAL ACTIVITY

The compounds were applied to the following species Lettuce (LT), Tomato(TO), Arena fatua (Av) and Setaria viridis (St) using a travelling boomtrack sprayer at a volume equivalent to 1000 l ha⁻¹ and atconcentrations corresponding to application rates 10 kg ha⁻¹.Assessments were made for pre-emergence activity 17-20 days after directspraying onto the seed, the seed having been covered with a compost forthat period. Assessments were also made for post-emergence activity 13days after spraying onto young plants.

The assessment scale used was as follows:

0=0-25% damage

1=26-50% damage

2=51-75% damage

3=76-100% damage

The results of this test are shown in Table V.

                  TABLE V                                                         ______________________________________                                        COM-    PRE OR POST  DAYS                                                     POUND   EMERGENCE    AFTER    TEST PLANTS 4                                   NO.     APPLICATION  TEST     Lt  To   Av   St                                ______________________________________                                        72      Post         13       3   3    3    3                                         Pre          17       3   3    0    2                                 73      Post         13       3   3    3    3                                         Pre          20       3   3    3    3                                 76      Post         13       0   0    0    0                                         Pre          20       0   0    0    0                                 75      Post         13       2   1    0    0                                         Pre          20       3   2    0    0                                 79      Post         13       3   3    3    3                                         Pre          20       3   3    3    3                                 80      Post         13       3   3    3    3                                         Pre          20       3   3    3    3                                 82      Post         13       3   3    2    3                                         Pre          17       3   3    2    3                                 81      Post         13       0   0    0    0                                         Pre          17       0   0    0    0                                 77      Post         13       3   3    1    1                                         Pre          17       3   3    0    0                                 78      Post         13       3   3    0    0                                         Pre          20       3   3    0    0                                 ______________________________________                                    

The herbicidal activity of the others of compounds was tested asfollows:

Each compound in the appropriate concentration was incorporated into a4% emulsion of methyl cyclohexanone and a 0.4% blend of 3.6 parts Tween20 and 1 part Span 80. Tween 20 is a Trade Mark for a surface activeagent comprising a condensate of 20 molar proportions of ethylene oxidewith sorbitan laurate. Span 80 is a Trade Mark for a surface-activeagent comprising sorbitan monolaurate. Formulation was effected bydissolving the compound in the requisite amount of solvent/surfactantblend. If necessary glass beads were added, the total liquid volumeadjusted to 5 ml with water and the mixture shaken to effect completedissolution of the compound. The formulation so prepared, after removalof beads where necessary, was then diluted to final spray volume (45 ml)with water.

The spray compositions so prepared were sprayed onto young pot plants(post-emergence test) at a rate equivalent to 1000 liters per hectare.Damage to plants was assessed 13 days after spraying by comparison withuntreated plants, on a scale of 0 to 5 where 0 is 0-10% damage, 1 is 11to 25% damage, 2 is 26-50% damage, 3 is 51-80% damage, 4 is 81-95%damage and 5 is 96-100% damage.

In a test carried out to detect pre-emergence herbicidal activity, seedsof the test species were placed on the surface of plastic trays ofcompost and sprayed with the compositions at the rate of 1000 liters perhectare. The seeds were then covered with further compost. 20 days afterspraying, the seedlings in the sprayed plastic trays were compared withthe seedlings in unsprayed control trays, the damage being assessed onthe same scale of 0 to 5.

The results of the tests are given in Table VI below.

                                      TABLE VI                                    __________________________________________________________________________            RATE OF  PRE- OR                                                      COMPOUND                                                                              APPLICATION                                                                            POST-EMERGENCE                                               NO.     kg/1ha   APPLICATION TEST PLANTS (see Table VII)                      __________________________________________________________________________                                 Sb                                                                              Rp                                                                              Ct                                                                              Sy                                                                              Mz Ww Rc Bd                                                                              Ip                                                                              Am Pi                                                                              Ca                     __________________________________________________________________________    4       4        Pre         3 1 --                                                                              0 1  0  0  1 0 0  1 3                                       Post        3 3 3 2 3  2  0  3 3 4  3 4                      3       4        Pre         3 3 1 0 0  0  0  0 --                                                                              0  --                                                                              0                                       Post        2 3 2 2 3  2  1  1 1 4  1 3                      5       4        Pre         4 0 1 2 1  0  1  2 0 1  0 3                                       Post        1 0 0 0 0  0  0  1 0 0  0 0                      __________________________________________________________________________                                 Ga                                                                              Xa                                                                              Xs                                                                              Ab                                                                              Co Av Dg Al                                                                              St                                                                              Ec                                                                              Sh                                                                              Ag                                                                              Cn                    __________________________________________________________________________    4       4        Pre         0 3 --                                                                              5 0  0  0  0 1 0 0 0 3                                      Post        0 --                                                                              3 3 3  2  4  2 3 3 2 1 1                     3       4        Pre         0 2 --                                                                              2 0  0  0  0 3 0 2 0 2                                      Post        1 --                                                                              1 2 2  0  3  1 0 2 2 2 0                     5       4        Pre         1 2 --                                                                              3 2  0  0  0 0 0 0 0 0                                      Post        0 --                                                                              0 0 0  0  0  0 0 0 0 0 0                     __________________________________________________________________________

TABLE VII Abbreviations Used for Test Plants

Sb--Sugar beet

Rp--Rape

Ct--Cotton

Sy--Soybean

Mz--Maize

Ww--Winter wheat

Rc--Rice

Bd--Bidens pilosa

Ip--Ipomoea purpurea

Am--Amaranthus retroflexus

Pi--Polygonum aviculare

Ca--Chenopodium album

Ga--Galium aDarine

Xa--Xanthium spinosum

Xs--Xantbium strumarium

Ab--Abutilon theophrasti

Co--Cassia obtusifolia

Av--Avena fatua

Dg--Digitaria sanguinalis

Al--Alopecurus myosuroides

St--Setaria viridis

Ec--Echinchloa crus-galli

Sh--Sorghum halepense

Ag--Agropyron repens

Cn--cyperus rotundus

We claim:
 1. A compound of formula (I): ##STR148## or an agriculturallyacceptable salt, enamine, acrylate, sulphonate, carbamate or etherderivative thereof; wherein X, X¹ and X² are independently oxygen orsulphur, R¹ is a thienyl, furyl, indolyl or benzothienyl group, and Y isa C₂ -C₄ alkylene group which is optionally substituted by oxo,mercapto, halo, nitro, cyano, amino, mono- or di-alkylamino, amido,alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkoxy phenyl,naphthyl, hydroxy, alkoxy, alkoxycarbonyl, alkylcarbonyl, mono- ordialkylcarbamoyl, alkythio, alkylsulphinyl, alkylsulphonyl,sulphonamido, alkylcarbonyloxy, alkyl carbonylamino, pyridyl or thienyland which may also have a single hetero atom optionally interposedbetween adjacent carbons of the alkylene group, said hetero atom beingan oxygen atom, a sulphur atom in a group ##STR149## or an optionallyalkyl- or alkoxy-substituted nitrogen atom, wherein p is 0, 1 or
 2. 2. Acompound according to claim 1 wherein R¹ is selected from ##STR150##wherein R⁵ is hydrogen or C₁ C₄ alkyl or phenyl; R⁶, R⁷ and R⁸independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4)haloalkoxy; (5) C₁ -C₄ alkoxy; (6) cyano; (7) nitro; (8) C₁ -C₄haloalkyl; (9) R⁹ SOn-- wherein n is the integer(a) C₁ -C₄ alkyl; (b) C₁-C₄ alkyl substituted with halogen, cyano, C₁ -C₂ alkoxy or C₁ -C₂alkylthio; (c) phenyl; or (d) benzyl; (10) --NR¹⁰ R¹¹ wherein R¹⁰ andR¹¹ independently are hydrogen or C₁ -C₄ alkyl; (11) R¹² C(O)-- whereinR¹² is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) --SO₂ NR¹⁰ R¹¹ wherein R¹⁰and R¹¹ are as defined above; or (13) --N(R¹⁰)C(O)R¹¹ wherein R¹⁰ andR¹¹ are as defined above.
 3. A compound according to claim 1 wherein Yis ##STR151## wherein R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ are independentlyselected from hydrogen, C₁₋₄ alkyl, C₁₋₄ alkanoyl or --CO₂ R²² whereinR²² is C₁₋₄ alkyl or R¹⁶ and R¹⁷ or R¹⁸ and R¹⁹ or R²⁰ and R²¹ togetherwith the carbon atom to which they are attached form a C₃₋₆ cycloalkylring; q is 0 or 1; and R²³ is alkyl or alkoxy.
 4. A compound accordingto claim 3 wherein R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ are hydrogen ormethyl.
 5. A compound according to claim 1 of formula (IA) ##STR152##wherein R¹⁶, R¹⁷, R²⁰ and R²¹ are hydrogen or methyl and R²⁵ is indolylor benzothienyl.
 6. A herbicidal composition comprising a compound offormula (I) as defined in claim 1 in combination with a carrier ordiluent.
 7. A method of killing or controlling unwanted plant specieswhich method comprises applying to the plant or to the locus thereof acompound of formula (I) as defined in claim 1.